Zn DIFFUSION INTO GAP

ABSTRACT

Zinc is diffused into N type gallium phosphide to form a PN junction therein. The zinc diffusion takes place in vacuum at temperatures between about 800*-950* C. from a ZnP2 source.

0 United States Patent 11 1 3,653,989 Widmer 1 5] Apr. 4, 1972 54] ZN DIFFUSION INTO GAP 3,239,393 3/1966 Dill, Jr .,..148/189 3,305,412 2 1967 P 11 ....148 189 Inventor: Erhard Widmer, Wuerenlos, SWit- 3 1 g 1 Zerland 3,573,114 3/1971 Marinace ..l48/l89 [73] Assignee: RCA Corporation Primary Exammer-L. Dewayne Rutledge [22] Filed: Apr. 2, 1970 Assistant ExaminerG. K.'White pp No: 25,225 Attorney-Glenn H. Bruestle [57] ABSTRACT [52] [1.8. Ci ..l48/l89, 148/186, 317/234 Zinc is diff d i N e gallium phosphide to form a PN [51] Int. Cl. .1101] 7/44 junction therein The zinc diff i takes place in vacuum at Fleld of Search temperatures between about 800 950 from 3 2 11 source. 56] References Cited 8 Claims, 6 Drawing Figures UNITED STATES PATENTS Patented April 4, 1972 3,653,989

2 Shah-Shut l ZN DIFFUSION INTO GAP BACKGROUND OF THE INVENTION This invention relates to the formation of a PN junction in N type semiconducting gallium phosphide. Gallium phosphide having a PN junction is useful, for example, as a light emitting diode. In the manufacture of light emitting diodes, zinc is diffused into N type gallium phosphide to form a PN junction therein. In the past, it has been difficult obtain a high quality smooth or regular junction. That is, a junction which is essentially free of sharp spikes. The junctions formed by prior art techniques are generally highly irregular as can be seen with reference to FIGS. 1-3. In orderto obtain reproducible and uniform operating characteristics in the GaP junction devices, it is important to obtain a smooth or regular junction.

SUMMARY OF THE INVENTION Amethod of diffusing zinc into the gallium phosphide by heating the GaP in the vapors produced from ZnP The process enables the formation of a GaP diode having a smooth PN junction, free of an intrinsic region, which is characterized by the function 1/C2 a V at low voltages and l/C3 a V at higher voltages where C is the capacitance of the diodeand V is the applied voltage.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1-4 are photographs of PN junctions produced in GaP by zinc diffusion from various sources.

FIG. 5 is a graph showing the junction depth in GaP as a function of the square root of diffusion time ofZn from a ZnP source at a temperature of 850 C.

FIG. 6 is a semilogarithmic plot showing the junction depth in GaP as a function of diffusion temperature of Zn from a ZnP source normalized for a 1 hour diffusion time.

7 DESCRIPTION OF THE PREFERRED EMBODIMENT I have discovered that very smooth planar PN junctions can be formed in gallium phosphide by the diffusion of zinc into N type GaP from a ZnP source.

Referring to FIGS. 1-4 there is shown PN junctions produced by the diffusion of zinc into GaP from various sources of zinc. The junctions are made visible under strong illurnination by etching a cleaveddiode in a 1:1 etch solution of H 0 and HF. The junction shown in FIG. 1 was produced by diffusing zinc from a pure zinc source at a concentration of l mg./cm. at 800 C. for 2 hours. The concentration as expressed herein is the weight of the zinc source material divided by the volume of the ampoule in which the diffusion iscarried out. The junction shown in FIG. 2 is the. result of diffusion from a source consisting of Zn (1 mgJcms") plus phosphorous (0:13 mg./cm. at 800 C. for 2 hours. The junction shown in FIG. 3 is the result of diffusion from a source consisting of Zn P (2 mg./cm. at=850 C. for 2 hours. The junctionshown in FIG. 4 is the result of diffusion from a source consisting of ZnP (2 mg./cm. at;850PC for 2 hours.

Itcan readily be seen from these figures that only diffusion: ofZnfrom the ZnP source resulted in a highly smooth flat junction essentially free of irregularities.

The compound, ZnP is known to exist in both a red tetragonal form and a black monoclinic form. Forms of the compound are equally suitable for use as a. diffusion source since it is the chemical composition rather than the crystal structure of the compound which is of prime importance.

A typical GaP useful for producing the diodes is selenium doped N type material grown epitaxially on (100) crystallographically oriented GaAs substrates, such materialcanbe. grown by the hydride technique reported by Tietjen and Amick in the Journal of the Electrochemical Society, I 13, 724, (I966). Alternatively, for. example, one canuse GaPdoped with sulfur. The GaP can also be prepared by other growth.

techniques such as vapor or liquid phase epitaxy.

Prior to diffusion, the GaAs substrate is preferably removed from the GaP such as with a 5 percent aqueous solution of a 5:l weight ratio mixture of NaOH and H 0 The GaP is preferably etched prior to diffusion to provide a clean surface. This may be accomplished by etching for 1 minute at room temperature in a 2:] solution of HCl and HNO The GaP and ZnP- are then placed at different ends of a cleaned quartz ampoule. A vacuum of about 10 torr is, provided within the ampoule.

The ampoule is then vacuum sealed. Typical diffusions are made at temperatures ranging from about 800-950 C. for l-9 hours depending upon the desired zinc concentration in the diode and the desired. junction depth. In any event the temperature should be below the melting point of GaP. The amount of ZnP used is based upon the: volume of the ampoule and is typically about 2-6 mg./cm.", however, this is not critical. It is preferred to keep the temperature of the ZnP lower then that of the GaP. For example, a temperature difference of about 5l0 C. is suitable. After diffusion, the ampoule is preferably quick-cooled so that the material in the gas phase condenses on the source end of the ampoule.

No erosion of the GaP was observed for diffusions at temperaturesbetween 800-950 C. However, some color change of the Ga? is noted in diffusions above about b 875 C. resulting in an opaque appearance. This is due to the high zinc concentrations obtained at these temperatures. Consequently, preferred diffusion temperatures are from 800-8 75 C.

The dependence of the diffusion depth as a function of the square root of time is shown in FIG. 5 for diffusions carried out at 850 C. The linear dependence shown indicates the process is readily controllable.

A semilogarithmic plot of junction depth versus reciprocal temperature is shown in FIG. 6 normalized for 1 hour diffusion times. This indicates that the junction depth is also readily controllable and determinable by a variation in diffusion temperature.

Diodes having a step junction characteristic at a small reverse bias, that is, less than 2.5 volts and a linear. graded junction characteristic at a higher reverse bias can be produced by the novel diffusiontechnique. In a step junction, the reciprocal of thesquare of the diode capacitance is proportional to the applied voltage. In a linearly graded junction the reciprocal of the cube of the capacitance is proportional to the bias voltage. In addition, no intrinsic layer is present in these diodes.

Iclaim:

1. A process for diffusing zinc into GiaP comprising heating GaP in the vapors produced from ZnP 2. A process for forming a PN junction in GaP comprising the step of diffusing zinc from a ZnP source of zinc into N type GaP.

3. The process for forming a PN junction in GaP recited in claim 2 wherein said N-type GaP and said ZnP zinc source are heated together in an evacuated container.

4. A process for forming a PN junction in GaP comprising the steps of enclosing N type Ga? and ZnP in an evacuated chamber and heating said chamber to a temperature of between 800-950 C. for a time sufficient for zinc to diffuse into said N type GaP so as to forma PN junction therein.

5. A process for forming a PN' junction in GaP comprising the steps of enclosingN type GaP and ZnP in an evacuated chamber, said N type GaP and said ZnP being separated from each other, heating said chamber and its contents to a temperature below the melting point of said GaP but sufficient to diffusezinc therein to form said junction, the temperature of said ZnP beingbelow the temperature of said GaP, and diffusing zinc into said GaP for a time sufficient to form a PN junction therein may desired depth.

6. The process recited in claim 5 wherein the temperature of said Ga? and ZnP is from 800-950 C.

7. The process recited in claim 5 wherein said evacuated chamber is at a pressure of 'about 10 torr. and wherein the Ga? and ZnP, areheated to a temperature of between800" and 875 C., the temperature of said ZnP being from 5l0 C. below the temperature of said GaP.

8. The process recited in claim 7 wherein said N type 6a? is epitaxially grown selenium doped GaP Patent No.

' Attest:

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,653,989 Dated April 4, 19,72

Inventoflg) Alois Erhard Widmer It is certified that. error appears in the aboveidentified patent and that said Letters Patent are hereby corrected as shown below:

ln the title, "ZN" should read -Zn-- and "GAP" should read GaP--. In Column 2, line 19, "then" should read --than line 25 delete "b" after "about" line 67 delete "junction" and insert -ZnP Signed and sealed this 1st day of August 1972.

(SEAL) EDWARD M.FLbJTCHER ,JR. ROBERT GOTTSCHALK Commissioner of Patents Attesting Officer USCOMM'DC 50376-P69 U.S. GOVERNMENT PRINTING OFFICE: [969 0-366-334 FORM PC4050 (10-69) 

2. A process for forming a PN junction in GaP comprising the step of diffusing zinc from a ZnP2 source of zinc Into N type GaP.
 3. The process for forming a PN junction in GaP recited in claim 2 wherein said N type GaP and said ZnP2 zinc source are heated together in an evacuated container.
 4. A process for forming a PN junction in GaP comprising the steps of enclosing N type GaP and ZnP2 in an evacuated chamber and heating said chamber to a temperature of between 800*-950* C. for a time sufficient for zinc to diffuse into said N type GaP so as to form a PN junction therein.
 5. A process for forming a PN junction in GaP comprising the steps of enclosing N type GaP and ZnP2 in an evacuated chamber, said N type GaP and said ZnP2 being separated from each other, heating said chamber and its contents to a temperature below the melting point of said GaP but sufficient to diffuse zinc therein to form said junction, the temperature of said ZnP2, being below the temperature of said GaP, and diffusing zinc into said GaP for a time sufficient to form a PN junction therein at any desired depth.
 6. The process recited in claim 5 wherein the temperature of said GaP and ZnP2 is from 800*-950* C.
 7. The process recited in claim 5 wherein said evacuated chamber is at a pressure of about 10 6 torr and wherein the GaP and ZnP2 are heated to a temperature of between 800* and 875* C., the temperature of said ZnP2 being from 5*-10* C. below the temperature of said GaP.
 8. The process recited in claim 7 wherein said N type GaP is epitaxially grown selenium doped GaP. 